EP0017948A1 - Procédé de préparation de polyuréthanes alvéolaires - Google Patents

Procédé de préparation de polyuréthanes alvéolaires Download PDF

Info

Publication number
EP0017948A1
EP0017948A1 EP80101989A EP80101989A EP0017948A1 EP 0017948 A1 EP0017948 A1 EP 0017948A1 EP 80101989 A EP80101989 A EP 80101989A EP 80101989 A EP80101989 A EP 80101989A EP 0017948 A1 EP0017948 A1 EP 0017948A1
Authority
EP
European Patent Office
Prior art keywords
tertiary amines
weight
neutral
hydroxyl
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP80101989A
Other languages
German (de)
English (en)
Other versions
EP0017948B1 (fr
Inventor
Hans-Otto Fick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to AT80101989T priority Critical patent/ATE4119T1/de
Publication of EP0017948A1 publication Critical patent/EP0017948A1/fr
Application granted granted Critical
Publication of EP0017948B1 publication Critical patent/EP0017948B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0016—Foam properties semi-rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0058—≥50 and <150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/60—Compositions for foaming; Foamed or intumescent adhesives

Definitions

  • the invention relates to a process for the production of semi-hard and hard polyurethane foams, neutral, acidic or basic salts of hydroxyl-containing secondary and / or tertiary amines and naphthenic acids or mixtures of the salts mentioned and conventional polyols being used as the polyhydroxy compounds.
  • salts of secondary or tertiary amines which may have bound hydroxyl groups, and monocarboxylic acids, polycarboxylic acids, sulfonic acids or acidic sulfuric acid esters in amounts of 1 to 10% by weight, based on the polyhydroxy compound, are used to produce polyurethane foams the polyurethane reaction, used as activators.
  • hydroxyl-containing salts the OH group is masked by addition or condensation reactions before the urethane reaction, according to the examples.
  • Fatty acids, fatty acid esters, fatty acid amides or salts of fatty acids can also be used to produce polyurethane foams.
  • neutral, water-containing salts of hydroxy fatty acids such as hydroxystearic acid, ricinoleic acid and castor oil, and secondary and tertiary amines are preferably used for the production of foams.
  • amides of fatty acids with 8 to 24 carbon atoms and dialkanolamines which can also contain salts of dialkanolamine and fatty acid and fatty acid esters, can also be used for this.
  • the salts themselves form extremely brittle foams that often collapse.
  • polyurethane plastics with a skeletal structure, which instead of cell walls only have cell bridges are also produced from polyisocyanates and castor oil in the presence of monoalcohols having 1 to 18 carbon atoms or monocarboxylic acids having 2 to 18 carbon atoms.
  • the object of the present invention was to bring the naphthenic acids isolated from petroleum, which are largely burned, to commercial use. It should also be tried to use the extremely inexpensive naphthenic acid as a polyol component for the production of polyurethane foams, the usual poly All or part of the oils are replaced by naphthenic acid, its derivatives or salts.
  • This object was achieved by a process for the production of semi-hard and hard polyurethane foams from polyhydroxy compounds, organic polyisocyanates, blowing agents and, if appropriate, catalysts, auxiliaries and additives, which is characterized in that neutral, acidic or basic salts from hydroxyl-containing secondary compounds are used as polyhydroxy compounds and / or tertiary amines and naphthenic acids are used.
  • the polyurethane foams that can be produced according to the invention are surprisingly almost odorless. Due to the composition of the naphthenic acids from aliphatic, mono- and bicyclic saturated monofunctional carboxylic acids, which also varies in certain areas depending on the country of origin, it was surprising that the reaction of the salts described above with organic polyisocyanates leads to crosslinked foams with good properties. It was particularly surprising that the hard polyurethane foams produced according to the invention harden very quickly and are therefore suitable for the production of sandwich panels at high speed.
  • the salts also have a certain foam-stabilizing and pore structure-influencing effect, so that auxiliaries and additives which give the effects mentioned can be dispensed with in whole or in part, if appropriate.
  • neutral, acidic or basic salts of hydroxyl-containing secondary and / or tertiary amines and naphthenic acids are used as polyhydroxy compounds to produce the semi-hard and hard polyurethane foams. turns.
  • the definition "neutral, acidic or basic salts'" is to be understood here in the sense that the components are present in an equivalent quantity ratio in the case of a neutral salt, the acid is present in the case of an acid salt, and the base is in excess in the case of a basic salt.
  • the definition is not intended to give any indication of the acidity or basicity of the salts.
  • neutral and / or basic salts, in particular basic salts are preferably used.
  • the secondary and tertiary amines containing hydroxyl groups which can be used according to the invention must be at least difunctional.
  • amines which contain at least one secondary amino group and at least one hydroxyl group bonded or amines which have at least one tertiary amino group, at least one hydroxyl group and, if only one hydroxyl group is present, additionally at least one further radical having a hydrogen atom which is reactive toward isocyanates for example have an SH, NH and / or NH 2 group.
  • compounds which have bonded a secondary and tertiary amino group in addition to at least one hydroxyl group or mixtures of secondary and tertiary amines containing hydroxyl groups are also suitable.
  • Examples include secondary amines, for example N-alkylalkanolamines having 1 to 4 carbon atoms in the alkyl radical, such as N-methylethanolamine, N-butylethanolamine, N-ethylpropanolamine and N-methylpropanolamine, dialkanolamines, such as diethanolamine and Diisopropanolamine, tertiary amines, for example N-alkyl-dialkanolamines having 1 to 4 carbon atoms in the alkyl radical, such as N-methyl-diethanolamine, N-methyldiisopropanolamine, N-ethyl-diethanolamine, N-ethyl-diisopropanolamine and N-butyl-diethanolamine; Trialkanolamines such as triethanolamine, triisopropanolamine; N, N, N ', N'-tetrakis ( ⁇ -hydroxyethyl) ethylene diamine, N, N, N, N
  • the hydroxyl-containing secondary and / or tertiary amines can be used as such or in the form of mixtures.
  • Dialkanolamines in particular diethanolamine, trialkanolamines, in particular triethanolamine, N, N, N ', N'-tetrakis - ( ⁇ -hydroxypropyl) ethylenediamine, N, N, N', N ", N” -pentakis ( ß - Hydroxyethyl) -diethylenetriamine, secondary and / or tertiary amino group-containing condensation products from aliphatic diamines and ethylene oxide and / or propylene oxide and secondary and / or tertiary amino group-containing polyesterols, in particular from aliphatic dicarboxylic acids and isopropanolamine mixtures.
  • Naphthenic acids in the sense of the invention are acids and acid mixtures with the general formulas C n H 2n-1 COOH and C n H 2n-3 COOH which occur in petroleum. They are usually obtained by extraction with alkali and acidification of the alkaline solution in the form of a brown to black, viscous product and usually still contain certain proportions of neutral oils. Naphthenic acids are saturated cyclic carboxylic acids which, depending on the origin of the petroleum, contain more or less large amounts of linear aliphatic carboxylic acids of the formula C n H 2n + 1 COOH.
  • naphthenic acids In naphthenic acids, a distinction is made between monocyclic carboxylic acids of the formula C n H 2n-1 COOH and bicyclic carboxylic acids of the formula C n H 2n-3 COOH.
  • the monocyclic carboxylic acids begin with the simplest naphthenic acid, the cyclopentane carboxylic acid and increase up to compounds with 20 carbon atoms. They are almost always mixed with carboxylic acids of the bicyclic series C n H 2n-3 COOH (n ⁇ 12).
  • the naphthenic acids can be purified using known methods. Corresponding processes are described, for example, in the monograph "Naphthenic Acids and Naphthenates" by WF Maass, E. Buchspiess-Paulentz and F. Stinsky, Publishing House for Chemical Industry H. Ziolkowsky KG, Augsburg, 1961. Both distilled naphthenic acids and the inexpensive technical ones are suitable Qualities. Commercially available technical naphthenic acids are
  • the naphthenic acids which can be used according to the invention have acid numbers from 60 to 350, preferably from 90 to 280, and densities at 15 ° C. from 0.92 to 1.00, preferably from 0.96 to 0.995 g / c m 3 .
  • the hydroxyl-containing secondary and tertiary amines and naphthenic acids are reacted at temperatures from 0 ° C. to 150 ° C., preferably from 10 ° C. to 100 ° C., in amounts such that 0 per carboxyl equivalent , 3 to 50, preferably 0.5 to 30, in particular 0.8 to 10 equivalent secondary and / or tertiary amino groups are present.
  • the salts of the starting components mentioned are preferably formed.
  • the process according to the invention is not adversely affected even by the formation of naphthenic acid amides or naphthenic acid esters in minor amounts.
  • conventional polyols include, for example, polyesterols and in particular polyetherols.
  • other hydroxyl-containing polymers with molecular weights of 200 to 6000 can also be used, for example polyacetals, such as polyoxymethylenes, polyesteramides and polycarbonates, in particular those prepared by transesterification of diphenyl carbonate with hexanediol-1,6.
  • Suitable polyesterols can be prepared, for example, from dicarboxylic acids, preferably aliphatic dicarboxylic acids, having 2 to 12, preferably 4 to 8, carbon atoms and polyhydric alcohols.
  • dicarboxylic acids preferably aliphatic dicarboxylic acids, having 2 to 12, preferably 4 to 8, carbon atoms and polyhydric alcohols.
  • examples include aliphatic dicarboxylic acids, such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and preferably succinic and adipic acid, and aromatic dicarboxylic acids, such as phthalic acid and terephthalic acid.
  • dihydric and polyhydric alcohols examples are: ethylene glycol, diethylene glycol, 1,2- or 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, trimethylolpropane, glycerol, pentaerythritol and Sucrose.
  • Ethylene glycol, propylene glycol and glycerin are preferably used.
  • Polyesterols which, by polycondensation of a dicarboxylic acid mixture which contains, based on the total weight of the dicarboxylic acids mentioned, contain 20 to 35% by weight, preferably 28 to 33% by weight, succinic acid, 35 to 50% by weight, preferably 40 to 45, have proven particularly useful %
  • mixtures of aliphatic diols and diamines and alkanolamine mixtures can also be used.
  • suitable isopropanolamine mixtures are those which contain 5 to 40% by weight, preferably 15 to 25% by weight diisopropanolamine and 95 to 60% by weight, preferably 85 to 75% by weight triisopropanolamine, based on the total weight of di- and triisopropanolamine contain, wherein the isopropanolamine mixture can still contain up to a maximum of 8% by weight, preferably up to 3% by weight, based on the total weight.
  • the isopropanolamine mixtures have hydrogen atoms which react with phthalic anhydride and correspond to an OH number of 830 to 950, preferably 860 to 920 (mg KOH / g).
  • Corresponding isopropanolamine mixtures can be obtained as by-products, for example, in the production of diisopropanolamine from ammonia or isopropanolamine and propylene oxide will.
  • the dicarboxylic acid mixture can also contain up to 5% by weight, preferably 2 to 3% by weight, based on the total weight, of impurities which essentially consist of imides of succinic and glutaric acid.
  • Dicarboxylic acid mixtures of the type mentioned can be obtained, for example, as by-products in the production of adipic acid by oxidation of cyclohexanol or cyclohexanone with nitric acid.
  • polyesterols which have molecular weights from 200 to 4000, preferably from 300 to 1500 and OH numbers from 40 to 800, preferably from 150 to 600, can be used individually or as mixtures with the neutral, acidic or basic naphthenic acid salts.
  • Suitable polyols for rigid foams are polyetherols with molecular weights from 200 to 2000, preferably from 300 to 1500 and OH numbers from 150 to 700, preferably from 300 to 600, for semi-rigid foams, polyetherols with molecular weights from 1000 to 6000, preferably 2000 to 5000 and OH numbers from 25 to 600, preferably from 25 to 80 used.
  • the polyetherols are prepared by known processes from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical and a starter molecule which contains 2 to 8 active hydrogen atoms bound.
  • Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • starter molecules are: water, dicarboxylic acids, such as succinic, adipic, phthalic and terephthalic acid, optionally mono- and dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical, such as ethylenediamine, 1,2- or 1,3- Propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane, optionally alkyl-substituted dialkanolamines having 1 to 4 carbon atoms in the alkyl radical, such as diethanolamine, diisopropanolamine, N-methyl- and N-ethyl-diethanolamine; Trialkanolamines, such as triethanolamine and triisopropanolamine and preferably polyhydric alcohols, such as ethylene glycol, 1,2- or 1,3-propylene glycol, diethylene glycol,
  • Ethylene glycol, propylene glycols, glycerin, trimethylolpropane, sorbitol and sucrose are preferably used.
  • the polyetherols can be used individually or as mixtures with one another and with the polyesterols described above together with the naphthenic acid salts.
  • Di- to trifunctional polyetherols are preferably used for the production of semi-rigid foams, and tetra- to octa-functional polyetherols for hard foams.
  • crosslinking agents for the preparation of the polyurethane foams in addition to the neutral, acidic or basic salts of naphthenic acids or mixtures of the naphthenic acid salts with conventional polyols.
  • Suitable crosslinking agents are polyfunctional, in particular di- to tetrafunctional, compounds with molecular weights from 18 to less than 600, preferably from 60 to 300.
  • Suitable are, for example, di- and / or trihydric alcohols, such as ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, glycerol, di- ( ⁇ -hydroxyethyl) hydroquinone, diamines, such as ethylenediamine, 3,3'- di- or 3,3 ', 5,5'-tetrealkyl-substituted 4,4'-diamino-diphenylmethane with 1 to 4 carbon atoms in the alkyl radical, 3,3'-dichloro-4,4'-diamino-diphenylmethane and alkanolamines, such as diethanolamine and triethanolamine.
  • diamines such as ethylenediamine, 3,3'- di- or 3,3 ', 5,5'-tetrealkyl-substituted 4,4'-diamino-diphenylmethane with 1 to 4 carbon atom
  • Organic polyisocyanates of the formula R (NCO) n are suitable for producing the polyurethane foams, where R is polyvalent aliphatic, alkylaromatic or aromatic organic radicals or mixed radicals of this type and n is an integer whose value corresponds to the valence number of R and at least two is.
  • Typical organic polyisocyanates for the purposes of the invention include, for example, aromatic polyisocyanates, such as 2,4- and 2,6-tolylene diisocyanate, 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanates , Biphenyl diisocyanates, m- or p-phenylene diisocyanate and 1,5-naphthylene diisocyanate and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.
  • aromatic polyisocyanates such as 2,4- and 2,6-tolylene diisocyanate, 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanates , Biphenyl diisocyanates, m- or p-phenylene diisocyanate and 1,5-n
  • the crude and pure toluyien diisocyanates and mixtures of 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanates are preferably used.
  • the polyisocyanates can be used individually or as mixtures.
  • Blowing agents which can be used in the process according to the invention include water which reacts with isocyanate groups to form carbon dioxide.
  • the amounts of water which can expediently be used are 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, based on the weight of polyhydroxy compound. If necessary, larger amounts of water can also be used, but preferably not if heat insulation properties are of particular importance.
  • blowing agents which can be used which are preferably used, are low-boiling liquids which evaporate under the influence of the exothermic polyaddition reaction.
  • Liquids which are inert to the organic polyisocyanate and boiling points of not are suitable Have above 100 ° C at atmospheric pressure, preferably between -40 and + 50 ° C.
  • halogenated hydrocarbons such as methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, dichloromonomofluoromethane, dichlorotetrafluoroethane and 1,1,2-trichloro-1,2,2-trifluoroethane. Mixtures of these low-boiling liquids with one another and / or with other substituted or unsubstituted hydrocarbons can also be used.
  • low-boiling liquid for the production of foams depends on the foam density that is to be achieved and, if appropriate, on the use of water. In general, amounts of 5 to 40 percent by weight based on 100 parts by weight of organic polyisocyanate give satisfactory results.
  • the neutral, acidic or basic naphthenic acid salts which can be used according to the invention have a certain foam-stabilizing effect and influence the pore structure, so that such auxiliaries can be dispensed with in whole or in part in the production of the polyurethane foams.
  • surface-active substances are also used in the process according to the invention.
  • auxiliaries and additives can also be used. Examples include catalysts, plasticizers, flame retardants, hydrolysis protection agents, fungistatic and bacteriostatic substances, dyes, pigments and fillers.
  • the reaction mixture can be customary catalysts, for example tertiary Amines, such as dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N-methyl- or N-ethylmorpholine, dimethylpiperazine, pyridine, 1-azabicyclo- (3,3, O) -octane, dimethylaminoethanol, 1,2-dimethylimidazole and preferably triethylenediamine, and metal salts such as iron (II) chloride, zinc chloride and preferably tin (II) salts and dibutyltin dilaurate are added.
  • the amount to be used is determined empirically as a function of the activity of the selected catalyst or the catalyst mixture determined by constitution.
  • surface-active substances which serve to support the homogenization of the starting materials and, if appropriate, are also suitable for regulating the cell structure of the foams.
  • examples include siloxane-oxyalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or rizonoleic acid esters and Vietnamese red oil, which are used in amounts of 0.2 to 6 parts by weight per 100 parts by weight of polyhydroxy compounds.
  • plasticizer in the reaction mixture so that the tendency towards brittleness in the products is reduced.
  • Conventional plasticizers can be used, but it is particularly expedient to use agents which contain phosphorus and / or halogen atoms and thereby increase the flame resistance of the polyurethane plastics.
  • agents include tricresyl phosphate, tris-2-chloroethyl phosphate, tris-chloropropyl phosphate and tris-2,3-dibromopropyl phosphate.
  • re flame retardants can be used. So it has proven to be useful to improve the fire behavior of polyurethane foams according to DIN 4102, that is, to get from building material class B3 to building material class B2, buildable flame retardants, for example diethanolamino - methylphosphoric acid diethyl ester, 2,3-dibromopropanol or to use a halogen-containing polyol (commercial product 0 Ixol BP 401 from Solvay).
  • buildable flame retardants for example diethanolamino - methylphosphoric acid diethyl ester, 2,3-dibromopropanol or to use a halogen-containing polyol (commercial product 0 Ixol BP 401 from Solvay).
  • Inorganic flame retardants such as antimony trioxide, arsenic oxide, ammonium phosphate and calcium sulfate are also suitable for flame retarding the polyurethane foams.
  • the polyurethane foams according to the invention are produced by the prepolymer and preferably the one shot process.
  • the liquid starting materials can be supplied individually or, if the components are solid, in the form of solutions or suspensions and mixed intensively in the mixing chamber.
  • the two-component process and combine the mixture of polyhydroxy compound, blowing agent, optionally auxiliaries and additives to form component A and use the organic polyisocyanates as component B.
  • the semi-hard and hard polyurethane foams produced according to the invention have a density of 15 to 150 g / l.
  • the semi-hard foams are particularly characterized by their high toughness, low brittleness and good flow properties.
  • the hard foams have excellent compressive strengths and can be processed into sandwich panels in formulations for double belt systems at high production speeds.
  • component A consisting of with component B, consisting of a mixture of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (crude MDI) with an NCO content of 30%, intimately mixed and reacted in such an amount that the ratio of Zerewitinoff-active hydrogen atoms of the compounds of component A to NCO groups of component B is 1.0: 1.05.
  • component A consists of a mixture of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (raw MDI) with an NCO content of 30% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP80101989A 1979-04-17 1980-04-14 Procédé de préparation de polyuréthanes alvéolaires Expired EP0017948B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80101989T ATE4119T1 (de) 1979-04-17 1980-04-14 Verfahren zur herstellung von polyurethanschaumstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792915458 DE2915458A1 (de) 1979-04-17 1979-04-17 Verfahren zur herstellung von polyurethanschaumstoffen
DE2915458 1979-04-17

Publications (2)

Publication Number Publication Date
EP0017948A1 true EP0017948A1 (fr) 1980-10-29
EP0017948B1 EP0017948B1 (fr) 1983-07-13

Family

ID=6068506

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80101989A Expired EP0017948B1 (fr) 1979-04-17 1980-04-14 Procédé de préparation de polyuréthanes alvéolaires

Country Status (3)

Country Link
EP (1) EP0017948B1 (fr)
AT (1) ATE4119T1 (fr)
DE (2) DE2915458A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672694A1 (fr) * 1994-03-17 1995-09-20 Bayer Ag Procédé de préparation de polyuréthanes éventuellement cellulaires
WO1996033230A1 (fr) * 1995-04-18 1996-10-24 Unichema Chemie B.V. Materiau polymere

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1802500A1 (de) * 1967-10-12 1969-05-29 Eggers Lura Aldo Maria Andrea Polyurethane aus Fettsaeuren und Verfahren zur Herstellung derselben
DE1953637A1 (de) * 1969-10-24 1971-04-29 Bayer Ag Verfahren zur Herstellung von Schaumstoffen
DE2614203A1 (de) * 1975-10-30 1977-05-12 Dow Chemical Europ Verfahren zum herstellen von polyurethan-schaumstoffen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1802500A1 (de) * 1967-10-12 1969-05-29 Eggers Lura Aldo Maria Andrea Polyurethane aus Fettsaeuren und Verfahren zur Herstellung derselben
DE1953637A1 (de) * 1969-10-24 1971-04-29 Bayer Ag Verfahren zur Herstellung von Schaumstoffen
DE2614203A1 (de) * 1975-10-30 1977-05-12 Dow Chemical Europ Verfahren zum herstellen von polyurethan-schaumstoffen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672694A1 (fr) * 1994-03-17 1995-09-20 Bayer Ag Procédé de préparation de polyuréthanes éventuellement cellulaires
CN1071762C (zh) * 1994-03-17 2001-09-26 拜尔公司 制备可带微孔的聚氨酯的方法
WO1996033230A1 (fr) * 1995-04-18 1996-10-24 Unichema Chemie B.V. Materiau polymere

Also Published As

Publication number Publication date
EP0017948B1 (fr) 1983-07-13
DE2915458A1 (de) 1980-10-30
DE3064087D1 (en) 1983-08-18
ATE4119T1 (de) 1983-07-15

Similar Documents

Publication Publication Date Title
EP0111121B1 (fr) Mélanges liquides de polyisocyanates contenant des groupes uréthane à base de diisocyanate de diphénylméthane, procédé de préparation et utilisation pour la préparation de mousses flexibles de polyuréthane
EP0004618B1 (fr) Procédé de préparation de mousses souples ignifuges de polyuréthanes contenant des dérivés de l&#39;acide cyanique comme ignifugeant
EP0056121B1 (fr) Procédé pour la fabrication de mousses souples et flexibles en polyuréthane ainsi que les mélanges de polyester-polyol-polyéther-polyol utilisables pour celles-ci
EP0148381B1 (fr) Mélanges liquides de polyisocyanates contenant des groupes urée, procédé de sa préparation et son utilisation pour la préparation de matières plastiques de polyuréthane et/ou de polyisocyanurate compactes ou cellulaires, en particulier des mousses flexibles de polyuréthane
EP0250967B1 (fr) Procédé pour la fabrication d&#39;oligoesters portant des groupes hydroxyles et leur utilisation
EP0056122B1 (fr) Procédé pour la fabrication de mousses souples et flexibles en polyuréthane, ayant une résistance à l&#39;hydrolyse améliorée et une facilité de poinçonnage
EP0004617B1 (fr) Procédé de préparation de mousses de polyuréthane flexibles possédant des propriétés de support de charge et d&#39;absorption de chocs améliorées à base de MDI brut ayant une teneur de 55 à 85 pour cent en poids de diisocyanate de diphénylméthane et de polyesterols
EP0004879B1 (fr) Procédé de préparation de mousses de polyuréthane flexibles en utilisant comme polyisocyanate un mélange modifié par de l&#39;uréthane de diisocyanate de diphénylméthane et de polyméthylène-polyisocyanate de polyphényle ayant une teneur de 55 à 85 pour-cent en poids d&#39;isomères de diisocyanate de diphénylméthane
EP0499053A2 (fr) Procédé de préparation d&#39;élastomères de polyuréthane et compositions de polyoxybutylène-polyoxyalcoylène-glycols et de composés glycidiliques appropriées à ce procédé
EP0017947B1 (fr) Procédé de préparation de polyisocyanurates alvéolaires contenant des groupes uréthane
DE2539982A1 (de) Polyurethane und verfahren zu ihrer herstellung
DE2621582C2 (de) Verfahren zur Herstellung von flammfesten, keinen Rauch entwickelnden Polyurethanschaumstoffen
EP0099531B1 (fr) Solutions de silicates alcalins stabilisées, procédé pour leur préparation, leur utilisation pour la fabrication de matériaux mousses à partir d&#39;organosilicates et procédé pour la préparation de ces organosilicates mousses
EP0075758A1 (fr) Procédé de préparation de mousses élastiques flexibles de polyuréthane
EP0124071B1 (fr) Procédé de fabrication de polyuréthanes élastiques compacts ou cellulaires
EP0017948B1 (fr) Procédé de préparation de polyuréthanes alvéolaires
EP0069975B1 (fr) Procédé pour préparer des mousses ignifuges contenant des groupes polyuréthane et/ou polyisocyanurate
EP0082397B1 (fr) Procédé de production de mousses de polyuréthanne-polyisocyanurate
DE2704196A1 (de) Verfahren zur herstellung von polyurethanhartschaumstoffen
DE4112793A1 (de) Verfahren zur herstellung von hydrolysestabilen, estergruppen gebunden enthaltenden polyurethanen und phenylen-bis-oxazoline enthaltende polyurethan elastomere
EP0041618A2 (fr) Procédé de préparation de mousses de polyuréthane élastiques
DE1963189A1 (de) Verfahren zur Herstellung von flammfesten,Urethangruppen aufweisenden Schaumstoffen
DE19545550A1 (de) Lignin-haltige Isocyanat-Präpolymer-Mischungen, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Polyurethanen sowie Verfahren zur Herstellung der Polyurethane
EP0000468A1 (fr) Polyols contenant du chlore et des groupements esters à base d&#39;acide tétrachlorophtalique, leur préparation et utilisation pour la fabrication de mousses de polyuréthane ou de polyisocyanurate ignifuges
DE2239235A1 (de) Steife bzw. unbiegsame polyurethanschaumstoffpolyole

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT NL SE

17P Request for examination filed

Effective date: 19810404

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 4119

Country of ref document: AT

Date of ref document: 19830715

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3064087

Country of ref document: DE

Date of ref document: 19830818

ET Fr: translation filed
NLXE Nl: other communications concerning ep-patents (part 3 heading xe)

Free format text: ON 27 OCTOBER, 1983, NEW PAGE 15 OF THE TRANSLATION HAS BEEN RECEIVED

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840322

Year of fee payment: 5

Ref country code: DE

Payment date: 19840322

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19840326

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19840331

Year of fee payment: 5

Ref country code: BE

Payment date: 19840331

Year of fee payment: 5

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19860326

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19870430

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19890103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19890414

Ref country code: AT

Effective date: 19890414

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19890415

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19890430

Ref country code: CH

Effective date: 19890430

Ref country code: BE

Effective date: 19890430

BERE Be: lapsed

Owner name: BASF A.G.

Effective date: 19890430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19891101

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19891228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 80101989.4

Effective date: 19900412